CN105692575B - A kind of Application way of rock phosphate in powder - Google Patents
A kind of Application way of rock phosphate in powder Download PDFInfo
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- CN105692575B CN105692575B CN201610054867.4A CN201610054867A CN105692575B CN 105692575 B CN105692575 B CN 105692575B CN 201610054867 A CN201610054867 A CN 201610054867A CN 105692575 B CN105692575 B CN 105692575B
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/32—Phosphates of magnesium, calcium, strontium, or barium
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/18—Phosphoric acid
- C01B25/22—Preparation by reacting phosphate-containing material with an acid, e.g. wet process
- C01B25/2208—Preparation by reacting phosphate-containing material with an acid, e.g. wet process with an acid or a mixture of acids other than sulfuric acid
- C01B25/2212—Preparation by reacting phosphate-containing material with an acid, e.g. wet process with an acid or a mixture of acids other than sulfuric acid with hydrochloric acid or hydrogen chloride in aqueous medium
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/46—Preparation involving solvent-solvent extraction
- C01B25/461—Preparation involving solvent-solvent extraction the phosphoric acid present in the medium obtained after reaction being first extracted from the liquid phase formed or separated then re-extracted as free acid by using water or as a phosphate by using a basic compound
- C01B25/462—Preparation involving solvent-solvent extraction the phosphoric acid present in the medium obtained after reaction being first extracted from the liquid phase formed or separated then re-extracted as free acid by using water or as a phosphate by using a basic compound the extracting agent being alcohol or a mixture of alcohols
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/46—Preparation involving solvent-solvent extraction
- C01B25/461—Preparation involving solvent-solvent extraction the phosphoric acid present in the medium obtained after reaction being first extracted from the liquid phase formed or separated then re-extracted as free acid by using water or as a phosphate by using a basic compound
- C01B25/464—Preparation involving solvent-solvent extraction the phosphoric acid present in the medium obtained after reaction being first extracted from the liquid phase formed or separated then re-extracted as free acid by using water or as a phosphate by using a basic compound the extracting agent being an ether or a mixture of ethers
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/46—Preparation involving solvent-solvent extraction
- C01B25/461—Preparation involving solvent-solvent extraction the phosphoric acid present in the medium obtained after reaction being first extracted from the liquid phase formed or separated then re-extracted as free acid by using water or as a phosphate by using a basic compound
- C01B25/465—Preparation involving solvent-solvent extraction the phosphoric acid present in the medium obtained after reaction being first extracted from the liquid phase formed or separated then re-extracted as free acid by using water or as a phosphate by using a basic compound the extracting agent being an ester or a mixture of esters
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/46—Sulfates
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K21/00—Fireproofing materials
- C09K21/02—Inorganic materials
- C09K21/04—Inorganic materials containing phosphorus
Abstract
The invention discloses a kind of Application way of rock phosphate in powder, by rock phosphate in powder through crushing, the ground phosphate rock and hydrochloric acid obtained after levigate is at normal temperatures after 0.5~6h of stirring reaction, separation of solid and liquid, fluorine removal is carried out to liquid solution, removal of impurities, calcium phosphorus separation (precipitation, filtering, extraction, dry etc.) etc. processing, and further residual chloride calcium solution is handled, finally not only obtain fertilizer calcium hydrophosphate, calcium hydrophosphate fodder, phosphor nitrogen composite combustion inhibitor, the product such as tricalcium phosphate and calcium sulfate crystal whiskers, dilute hydrochloric acid solution is also obtained, phosphate rock-sulfuric acid powder process is returned after dilute hydrochloric acid solution rectifying is concentrated.The hydrochloric acid that the present invention uses can carry out following bad utilization, i.e. the present invention can generate hydrochloric acid, by obtained hydrochloric acid decomposing phosphate rock stone again, acidolysis cost is low, the phosphorus chemical products such as fertilizer calcium hydrophosphate, calcium hydrophosphate fodder, phosphor nitrogen composite combustion inhibitor, tricalcium phosphate and calcium sulfate crystal whiskers can also be obtained simultaneously, so that phosphorus ore comprehensive utilization ratio is high, it is good in economic efficiency.
Description
Technical field
The present invention relates to a kind of Application way of rock phosphate in powder, the utilization side for the rock phosphate in powder that particularly a kind of hydrochloric acid recycles
Method.
Background technology
With phosphoric acid and calcium chloride that the reacted product of rock phosphate in powder is highly-water-soluble, the difference with sulfuric acid process is not hydrochloric acid
Occur that calcium sulfate is covered in caused passivation phenomenon on undecomposed ground phosphate rock, therefore do not need ore grinding, technique mistake can be reduced
Journey energy consumption；The ability of decomposing phosphate rock by chlorhydric acid stone is strong, in general, low-grade block rock phosphate in powder have very high phosphorus dissolution rate,
Decomposing phosphate rock by chlorhydric acid also have be swift in response, resolution ratio it is high, the advantages that various ore deposits are applicable.Therefore, for China's phosphor resource
Sustainable use has greater significance.However, during decomposing phosphate rock by chlorhydric acid stone, hydrochloric acid is running stores so that acidolysis cost is higher.
The content of the invention
The purpose of the present invention, it is to provide a kind of Application way of rock phosphate in powder.The hydrochloric acid used in the inventive method can be carried out
Bad utilization is followed, i.e., present invention process can finally generate hydrochloric acid, and obtained hydrochloric acid is again returned into system decomposition rock phosphate in powder, acid
Solve cost it is low, while can also obtain fertilizer calcium hydrophosphate, calcium hydrophosphate fodder, phosphorus-nitrogen composite combustion inhibitor, tricalcium phosphate and
The phosphorus chemical products such as calcium sulfate crystal whiskers so that phosphorus ore comprehensive utilization ratio is high, good in economic efficiency.
What the present invention was realized in.A kind of Application way of rock phosphate in powder, comprises the following steps：
1st, by rock phosphate in powder through crushing, it is levigate after obtained ground phosphate rock and hydrochloric acid at normal temperatures after 0.5~6h of stirring reaction, Gu
Liquid separates, and obtains phosphoric acid and the solution A of calcium chloride；
2nd, defluorinating agent is added into solution A, it is stirring while adding, continue 0.5~2h of stirring after adding, stand, separation of solid and liquid,
Obtain solution B；
3rd, solution B is mixed with organic extractant and extracted, split-phase obtains oil phase X and aqueous phase Y, and oil phase X is stripped with pure water
Obtain phosphoric acid,diluted；The organic extractant is one or more of n-butanol, isoamyl alcohol, diisopropyl ether or tributyl phosphate；Or
Milk of lime is slowly added into solution B and adjusts pH value to 1.6~2.8, it is stirring while adding, continue 1~4h of stirring, mistake after adding
Filter, filter residue A1 and solution C are obtained, filter residue A1 is dried at 70~170 DEG C, obtains fertilizer calcium hydrophosphate；
4th, cleaner is added into solution C, it is stirring while adding, continue 0.5~3h of stirring after adding, filter, obtain solution D；
5th, solution D is heated to 20~80 DEG C, heated while stirring, be slow added into calcium containing compound adjust pH value to
4.5~6,2~6h is reacted, filtering, obtains filter residue B1 and solution F, filter residue B1 is dried at 70~170 DEG C, obtains feed grade phosphoric acid
Hydrogen calcium；Or by the molar ratio of phosphorus in solution D and melamine it is 0.5-1.5：0.5-4 adds solid melamine, reaction 0.5
After~3h, catalyst is added, continues 0.5~5h of reaction, then is warming up to 80~160 DEG C, adds melamine mole
0.5~10 times of reagent, continue 0.4~5h of stirring reaction, filtering, obtain filter residue C1 and solution G, filter residue C1 is at 70~170 DEG C
Lower drying, obtains phosphorus-nitrogen composite combustion inhibitor, and the reagent is bisphenol-A, phosphoric acid, urea, cyanuric acid, pentaerythrite or season penta 2
One or more of alcohol；
6th, milk of lime is slowly added into aqueous phase Y, solution F or solution G and adjusts pH value to 7-8, stirring while adding, reaction
90min~180min, filtering, filter residue D1 and Solution H are obtained, filter residue D1 is dried at 70~170 DEG C, obtains tricalcium phosphate；
7th, Solution H is heated to temperature as 20~80 DEG C, in the state of stirring, by calcium chloride in Solution H and sulfuric acid
Molar ratio is 1：0.8~2 adds sulfuric acid, reacts 1~4h, filtering, obtains filter residue E1 and dilute hydrochloric acid solution, filter residue E1 70~
Dried at 170 DEG C, obtain calcium sulfate crystal whiskers, phosphate rock-sulfuric acid powder in return to step (1) after dilute hydrochloric acid solution rectifying is concentrated.
In the Application way of foregoing rock phosphate in powder, the rock phosphate in powder described in step 1 is mid low grade phosphate rock stone or phosphorus concentrate,
The granularity of ground phosphate rock is less than 40 mesh after levigate, and concentration of hydrochloric acid is 15~37wt%, and addition is the 1.5~4 of ground phosphate rock quality
Times.
In the Application way of foregoing rock phosphate in powder, in step 2 add defluorinating agent amount for the fluorine-containing mole of ground phosphate rock 1~
4 times.
In the Application way of foregoing rock phosphate in powder, the defluorinating agent calculates by weight, by active silica 0.5-1.5
Part and sodium chloride 4-8 parts are made.
In the Application way of foregoing rock phosphate in powder, in step 4 add cleaner amount for ground phosphate rock quality 3wt ‰~
8wt‰。
In the Application way of foregoing rock phosphate in powder, the cleaner calculates by weight, by vulcanized sodium 0.5-1.5 parts and second
Edetate disodium 10-20 parts are made.
In the Application way of foregoing rock phosphate in powder, the calcium containing compound described in step 5 is lime stone, calcite, raw stone
One or more of ash or white lime.
In the Application way of foregoing rock phosphate in powder, the catalyst described in step 5 is urea, ammonia contracting urea, hydrazine hydrate, ethene
One or more of urea, ethyl carbamide or MU.
In the Application way of foregoing rock phosphate in powder, the addition of the catalyst is the 0.2~20% of melamine quality.
Compared with the prior art, the inventive method adds sulfuric acid into the Solution H of final gained, reaction, after filtering, can obtain
To dilute hydrochloric acid solution and filter residue, reaction system phosphate rock-sulfuric acid powder again is can return to after dilute hydrochloric acid solution rectifying concentration, is one and follows
Circulation journey, acidolysis cost are low.Filter residue and drying can obtain calcium sulfate crystal whiskers, and calcium sulfate crystal whiskers have dimensionally stable, intensity height, toughness
The excellent physical and chemical performances such as good, high-insulativity, abrasion performance, high temperature resistant, are widely used in rubber, papermaking, pitch, thermal insulating material
Material, fire-resistant heat insulating material, the high insulating materials etc. of infrared light reflecting material and covered electric cable.Salt in the inventive method step 1
Acid concentration is 15~37wt%, when the amount for adding hydrochloric acid is 1.5~4 times of ground phosphate rock quality, can obtain higher P2O5Decomposition
Rate, P2O5Resolution ratio typically more than 97%.Cleaner is added in step 4 into solution C, cleaner is vulcanized sodium and second two
When amine tetraacethyl disodium is made, the foreign ions such as arsenic in solution, lead, cadmium, iron, magnesium can be removed, and control vulcanized sodium and second two
The mass ratio of amine tetraacethyl disodium is 0.5-1.5:During 10-20, impurity-eliminating effect is preferable.Defluorinating agent is added in step 2, defluorinating agent is
When active silica and sodium chloride are made, the viscosity of phosphoric acid can be reduced, can also fully adsorb sludge particles, makes sedimentation abundant,
So that fluorine removing rate is higher, and it is 0.5-1.5 to control the mass ratio of active silica and sodium chloride：4-8, fluorine removal dosage
For 1~4 times of the fluorine-containing mole of ground phosphate rock when, defluorination effect is preferable, and fluoride removing rate is more than 95%.In addition, the inventive method is also
Fertilizer calcium hydrophosphate, calcium hydrophosphate fodder, phosphorus-nitrogen composite combustion inhibitor and tricalcium phosphate product etc. can be produced, is improved
The utilization rate of phosphorus, it is good in economic efficiency.
The present invention is further illustrated by the following examples, but not as limitation of the present invention.
Embodiment
Embodiment 1.
A kind of Application way of rock phosphate in powder, comprises the following steps：
1st, by rock phosphate in powder through crushing, it is levigate after obtained ground phosphate rock with after hydrochloric acid at normal temperatures stirring reaction 3h, solid-liquid divides
From obtaining phosphoric acid and the solution A of calcium chloride；Described rock phosphate in powder is phosphorus concentrate, and the granularity of ground phosphate rock is less than 40 mesh after levigate,
Concentration of hydrochloric acid is 25wt%, and addition is 2.5 times of ground phosphate rock quality；
2nd, defluorinating agent is added into solution A, it is stirring while adding, continue to stir 1.5h after adding, stand, separation of solid and liquid, obtain
Solution B；The defluorinating agent is mixed by active silica 10g and sodium chloride 60g；The amount for adding defluorinating agent contains for ground phosphate rock
2 times of fluorine mole；
3rd, it is 2 that milk of lime regulation pH value is slowly added into solution B, stirring while adding, continues to stir 2h, mistake after adding
Filter, obtains filter residue A1 and solution C；Filter residue A1 is dried at 100-120 DEG C, obtains fertilizer calcium hydrophosphate；
4th, cleaner is added into solution C, it is stirring while adding, continue to stir 1.5h after adding, filtering, obtain solution D；It is described
Cleaner is mixed by vulcanized sodium 10g and disodium ethylene diamine tetraacetate 150g；The amount for adding cleaner is ground phosphate rock quality
6.5wt‰；
5th, it is 1 by the molar ratio of phosphorus in solution D and melamine：2 add solid melamine, after reacting 1.5h, then
Catalyst is added, continues to react 2.5h, then is warming up to 100-120 DEG C, adds reagent, continues stirring reaction 2.5h, filtering, obtains
To filter residue C1 and solution G, filter residue C1 is dried at 100-120 DEG C, obtains phosphorus-nitrogen composite combustion inhibitor；The reagent be bisphenol-A,
Cyanuric acid, pentaerythrite and season pentanediol, the addition of reagent are 5 times of melamine mole, and described catalyst is water
Close hydrazine, ethylene urea and MU；The addition of catalyst is the 10% of melamine quality；
6th, milk of lime is slowly added into solution G and adjusts pH value to 7.5, it is stirring while adding, 145min is reacted, filtering, is obtained
To filter residue D1 and Solution H, filter residue D1 is dried at 90-110 DEG C, obtains tricalcium phosphate；
7th, Solution H is heated to temperature as 50-60 DEG C, in the state of stirring, by rubbing for calcium chloride in Solution H and sulfuric acid
Your ratio is 1：1.5 add sulfuric acid, react 2h, and filtering obtains filter residue E1 and dilute hydrochloric acid solution, and filter residue E1 is done at 110-120 DEG C
It is dry, calcium sulfate crystal whiskers are obtained, phosphate rock-sulfuric acid powder in return to step 1 after dilute hydrochloric acid solution rectifying is concentrated.
Embodiment 2.
A kind of Application way of rock phosphate in powder, comprises the following steps：
1st, by rock phosphate in powder through crushing, it is levigate after obtained ground phosphate rock with after hydrochloric acid at normal temperatures stirring reaction 6h, solid-liquid divides
From obtaining phosphoric acid and the solution A of calcium chloride；Described rock phosphate in powder is phosphorus concentrate, and the granularity of ground phosphate rock is less than 40 mesh after levigate,
Concentration of hydrochloric acid is 37wt%, and addition is 4 times of ground phosphate rock quality；
2nd, defluorinating agent is added into solution A, it is stirring while adding, continue to stir 1.5h after adding, stand, separation of solid and liquid, obtain
Solution B；The defluorinating agent is mixed by active silica 10g and sodium chloride 60g；The amount for adding defluorinating agent contains for ground phosphate rock
2 times of fluorine mole；
3rd, it is 2.8 that milk of lime regulation pH value is slowly added into solution B, stirring while adding, continues to stir 4h, mistake after adding
Filter, obtains filter residue A1 and solution C；Filter residue A1 is dried at 100-120 DEG C, obtains fertilizer calcium hydrophosphate；
4th, cleaner is added into solution C, it is stirring while adding, continue to stir 3h after adding, filtering, obtain solution D；It is described to remove
Miscellaneous dose is mixed by vulcanized sodium 15g and disodium ethylene diamine tetraacetate 200g；The amount for adding cleaner is ground phosphate rock quality
8wt‰；
5th, it is 1.5 by the molar ratio of phosphorus in solution D and melamine：4 add solid melamine, after reacting 5h, then
Catalyst is added, continues to react 5h, then is warming up to 100-120 DEG C, adds reagent, continues stirring reaction 5h, filtering, is filtered
Slag C1 and solution G, filter residue C1 are dried at 100-120 DEG C, obtain phosphorus-nitrogen composite combustion inhibitor；The reagent is bisphenol-A, cyanogen urine
Acid, pentaerythrite and season pentanediol, the addition of reagent are 10 times of melamine mole, and described catalyst is hydration
Hydrazine, ethylene urea and MU；The addition of catalyst is the 10% of melamine quality；
6th, milk of lime is slowly added into solution G and adjusts pH value to 8, it is stirring while adding, 180min is reacted, filtering, is obtained
Filter residue D1 and Solution H, filter residue D1 are dried at 160-170 DEG C, obtain tricalcium phosphate；
7th, Solution H is heated to temperature as 70-80 DEG C, in the state of stirring, by rubbing for calcium chloride in Solution H and sulfuric acid
Your ratio is 1：2 add sulfuric acid, react 4h, filtering, obtain filter residue E1 and dilute hydrochloric acid solution, and filter residue E1 is dried at 110-120 DEG C,
Calcium sulfate crystal whiskers are obtained, phosphate rock-sulfuric acid powder in return to step 1 after dilute hydrochloric acid solution rectifying is concentrated.
Embodiment 3.
A kind of Application way of rock phosphate in powder, comprises the following steps：
1st, by rock phosphate in powder through crushing, it is levigate after obtained ground phosphate rock and hydrochloric acid at normal temperatures after stirring reaction 0.5h, solid-liquid
Separation, obtains phosphoric acid and the solution A of calcium chloride；Described rock phosphate in powder is phosphorus concentrate, and the granularity of ground phosphate rock is less than 40 after levigate
Mesh, concentration of hydrochloric acid 15wt%, addition are 1.5 times of ground phosphate rock quality；
2nd, defluorinating agent is added into solution A, it is stirring while adding, continue to stir 0.5h after adding, stand, separation of solid and liquid, obtain
Solution B；The defluorinating agent is mixed by active silica 5g and sodium chloride 40g；The amount for adding defluorinating agent contains for ground phosphate rock
1 times of fluorine mole；
3rd, it is 1.6 that milk of lime regulation pH value is slowly added into solution B, stirring while adding, continues to stir 1h, mistake after adding
Filter, obtains filter residue A1 and solution C；Filter residue A1 is dried at 100-120 DEG C, obtains fertilizer calcium hydrophosphate；
4th, cleaner is added into solution C, it is stirring while adding, continue to stir 0.5h after adding, filtering, obtain solution D；It is described
Cleaner is mixed by vulcanized sodium 5g and disodium ethylene diamine tetraacetate 100g；The amount for adding cleaner is ground phosphate rock quality
3wt‰；
5th, it is 0.5 by the molar ratio of phosphorus in solution D and melamine：4 add solid melamine, after reacting 0.5h,
Catalyst is added, continues to react 0.5h, then is warming up to 100-120 DEG C, reagent is added, continues stirring reaction 0.4h, filter,
Filter residue C1 and solution G are obtained, filter residue C1 is dried at 100-120 DEG C, obtains phosphorus-nitrogen composite combustion inhibitor；The reagent is season penta
Tetrol and season pentanediol, the addition of reagent are 0.5 times of melamine mole, and described catalyst is hydrazine hydrate, ethene
Urea and MU；The addition of catalyst is the 0.2% of melamine quality；
6th, milk of lime is slowly added into solution G and adjusts pH value to 7, it is stirring while adding, 90min is reacted, filtering, is filtered
Slag D1 and Solution H, filter residue D1 are dried at 70-80 DEG C, obtain tricalcium phosphate；
7th, Solution H is heated to temperature as 20-30 DEG C, in the state of stirring, by rubbing for calcium chloride in Solution H and sulfuric acid
Your ratio is 1：0.8 adds sulfuric acid, reacts 1h, filtering, obtains filter residue E1 and dilute hydrochloric acid solution, and filter residue E1 is dried at 70-80 DEG C,
Calcium sulfate crystal whiskers are obtained, phosphate rock-sulfuric acid powder in return to step 1 after dilute hydrochloric acid solution rectifying is concentrated.
Embodiment 4.
A kind of Application way of rock phosphate in powder, comprises the following steps：
1st, by rock phosphate in powder through crushing, it is levigate after obtained ground phosphate rock with after hydrochloric acid at normal temperatures stirring reaction 3h, solid-liquid divides
From obtaining phosphoric acid and the solution A of calcium chloride；Described rock phosphate in powder is phosphorus concentrate, and the granularity of ground phosphate rock is less than 40 mesh after levigate,
Concentration of hydrochloric acid is 25wt%, and addition is 2.5 times of ground phosphate rock quality；
2nd, defluorinating agent is added into solution A, it is stirring while adding, continue to stir 1.5h after adding, stand, separation of solid and liquid, obtain
Solution B；The defluorinating agent is mixed by active silica 10g and sodium chloride 60g；The amount for adding defluorinating agent contains for ground phosphate rock
2 times of fluorine mole；
3rd, it is 2 that milk of lime regulation pH value is slowly added into solution B, stirring while adding, continues to stir 2h, mistake after adding
Filter, obtains filter residue A1 and solution C；Filter residue A1 is dried at 100-120 DEG C, obtains fertilizer calcium hydrophosphate；
4th, cleaner is added into solution C, it is stirring while adding, continue to stir 1.5h after adding, filtering, obtain solution D；It is described
Cleaner is mixed by vulcanized sodium 10g and disodium ethylene diamine tetraacetate 150g；The amount for adding cleaner is ground phosphate rock quality
6.5wt‰；
5th, solution D is heated to 40-50 DEG C, heated while stirring, be slow added into quick lime and adjust pH value to 5, react
4h, filtering, filter residue B1 and solution F are obtained, filter residue B1 is dried at 120~120 DEG C, obtains calcium hydrophosphate fodder；
6th, milk of lime is slowly added into solution F and adjusts pH value to 7.5, it is stirring while adding, 130min is reacted, filtering, is obtained
To filter residue D1 and Solution H, filter residue D1 is dried at 120~130 DEG C, obtains tricalcium phosphate；
7th, Solution H is heated to temperature as 40-50 DEG C, in the state of stirring, by rubbing for calcium chloride in Solution H and sulfuric acid
Your ratio is 1:1.5 add sulfuric acid, react 2h, and filtering obtains filter residue E1 and dilute hydrochloric acid solution, and filter residue E1 is done at 120~130 DEG C
It is dry, calcium sulfate crystal whiskers are obtained, phosphate rock-sulfuric acid powder in return to step 1 after dilute hydrochloric acid solution rectifying is concentrated.
Embodiment 5.
A kind of Application way of rock phosphate in powder, comprises the following steps：
1st, by rock phosphate in powder through crushing, it is levigate after obtained ground phosphate rock with after hydrochloric acid at normal temperatures stirring reaction 6h, solid-liquid divides
From obtaining phosphoric acid and the solution A of calcium chloride；Described rock phosphate in powder is phosphorus concentrate, and the granularity of ground phosphate rock is less than 40 mesh after levigate,
Concentration of hydrochloric acid is 37wt%, and addition is 4 times of ground phosphate rock quality；
2nd, defluorinating agent is added into solution A, it is stirring while adding, continue to stir 2h after adding, stand, separation of solid and liquid, obtain molten
Liquid B；The defluorinating agent is mixed by active silica 15g and sodium chloride 80g；The amount for adding defluorinating agent is fluorine-containing for ground phosphate rock
4 times of mole；
3rd, it is 2.8 that milk of lime regulation pH value is slowly added into solution B, stirring while adding, continues to stir 4h, mistake after adding
Filter, obtains filter residue A1 and solution C；Filter residue A1 is dried at 160-170 DEG C, obtains fertilizer calcium hydrophosphate；
4th, cleaner is added into solution C, it is stirring while adding, continue to stir 3h after adding, filtering, obtain solution D；It is described to remove
Miscellaneous dose is mixed by vulcanized sodium 15g and disodium ethylene diamine tetraacetate 200g；The amount for adding cleaner is ground phosphate rock quality
8wt‰；
5th, solution D is heated to 70-80 DEG C, heated while stirring, be slow added into quick lime and adjust pH value to 6, react
6h, filtering, filter residue B1 and solution F are obtained, filter residue B1 is dried at 160~170 DEG C, obtains calcium hydrophosphate fodder；
6th, milk of lime is slowly added into solution F and adjusts pH value to 8, it is stirring while adding, 180min is reacted, filtering, is obtained
Filter residue D1 and Solution H, filter residue D1 are dried at 160~170 DEG C, obtain tricalcium phosphate；
7th, Solution H is heated to temperature as 70-80 DEG C, in the state of stirring, by rubbing for calcium chloride in Solution H and sulfuric acid
Your ratio is 1:2 add sulfuric acid, react 4h, and filtering obtains filter residue E1 and dilute hydrochloric acid solution, and filter residue E1 is done at 160~170 DEG C
It is dry, calcium sulfate crystal whiskers are obtained, phosphate rock-sulfuric acid powder in return to step 1 after dilute hydrochloric acid solution rectifying is concentrated.
Embodiment 6.
A kind of Application way of rock phosphate in powder, comprises the following steps：
1st, by rock phosphate in powder through crushing, it is levigate after obtained ground phosphate rock and hydrochloric acid at normal temperatures after stirring reaction 0.5h, solid-liquid
Separation, obtains phosphoric acid and the solution A of calcium chloride；Described rock phosphate in powder is phosphorus concentrate, and the granularity of ground phosphate rock is less than 40 after levigate
Mesh, concentration of hydrochloric acid 15wt%, addition are 1.5 times of ground phosphate rock quality；
2nd, defluorinating agent is added into solution A, it is stirring while adding, continue to stir 2h after adding, stand, separation of solid and liquid, obtain molten
Liquid B；The defluorinating agent is mixed by active silica 15g and sodium chloride 80g；The amount for adding defluorinating agent is fluorine-containing for ground phosphate rock
4 times of mole；
3rd, it is 1.6 that milk of lime regulation pH value is slowly added into solution B, stirring while adding, continues to stir 1h, mistake after adding
Filter, obtains filter residue A1 and solution C；Filter residue A1 is dried at 70-80 DEG C, obtains fertilizer calcium hydrophosphate；
4th, cleaner is added into solution C, it is stirring while adding, continue to stir 0.5h after adding, filtering, obtain solution D；It is described
Cleaner is mixed by vulcanized sodium 5g and disodium ethylene diamine tetraacetate 100g；The amount for adding cleaner is ground phosphate rock quality
3wt‰；
5th, solution D is heated to 20-30 DEG C, heated while stirring, be slow added into quick lime and adjust pH value to 4.5, instead
2h is answered, is filtered, obtains filter residue B1 and solution F, filter residue B1 is dried at 70~80 DEG C, obtains calcium hydrophosphate fodder；
6th, milk of lime is slowly added into solution F and adjusts pH value to 7, it is stirring while adding, 90min is reacted, filtering, is filtered
Slag D1 and Solution H, filter residue D1 are dried at 70~80 DEG C, obtain tricalcium phosphate；
7th, Solution H is heated to temperature as 20-30 DEG C, in the state of stirring, by rubbing for calcium chloride in Solution H and sulfuric acid
Your ratio is 1:0.8 adds sulfuric acid, reacts 1h, and filtering obtains filter residue E1 and dilute hydrochloric acid solution, and filter residue E1 is done at 70~80 DEG C
It is dry, calcium sulfate crystal whiskers are obtained, phosphate rock-sulfuric acid powder in return to step 1 after dilute hydrochloric acid solution rectifying is concentrated.
Embodiment 7.
A kind of Application way of rock phosphate in powder, comprises the following steps：
1st, by rock phosphate in powder through crushing, it is levigate after obtained ground phosphate rock with after hydrochloric acid at normal temperatures stirring reaction 3h, solid-liquid divides
From obtaining phosphoric acid and the solution A of calcium chloride；Described rock phosphate in powder is phosphorus concentrate, and the granularity of ground phosphate rock is less than 40 mesh after levigate,
Concentration of hydrochloric acid is 25wt%, and addition is 2.5 times of ground phosphate rock quality；
2nd, defluorinating agent is added into solution A, it is stirring while adding, continue to stir 1.5h after adding, stand, separation of solid and liquid, obtain
Solution B；The defluorinating agent is mixed by active silica 10g and sodium chloride 60g；The amount for adding defluorinating agent contains for ground phosphate rock
2 times of fluorine mole；
3rd, solution B is mixed with organic extractant and extracted, split-phase obtains oil phase X and aqueous phase Y, and oil phase X is stripped with pure water
Obtain phosphoric acid,diluted；The organic extractant is n-butanol, isoamyl alcohol and diisopropyl ether；
4th, milk of lime is slowly added into aqueous phase Y and adjusts pH value to 7.5, it is stirring while adding, 125min is reacted, filtering, is obtained
To filter residue D1 and Solution H, filter residue D1 is dried at 120~130 DEG C, obtains tricalcium phosphate；
5th, Solution H is heated to temperature as 50~60 DEG C, in the state of stirring, by calcium chloride in Solution H and sulfuric acid
Molar ratio is 1：1.5 add sulfuric acid, react 2h, filtering, obtain filter residue E1 and dilute hydrochloric acid solution, filter residue E1 is at 130~140 DEG C
Dry, obtain calcium sulfate crystal whiskers, phosphate rock-sulfuric acid powder in return to step 1 after dilute hydrochloric acid solution rectifying is concentrated.
Embodiment 8.
A kind of Application way of rock phosphate in powder, comprises the following steps：
1st, by rock phosphate in powder through crushing, it is levigate after obtained ground phosphate rock with after hydrochloric acid at normal temperatures stirring reaction 6h, solid-liquid divides
From obtaining phosphoric acid and the solution A of calcium chloride；Described rock phosphate in powder is phosphorus concentrate, and the granularity of ground phosphate rock is less than 40 mesh after levigate,
Concentration of hydrochloric acid is 37wt%, and addition is 4 times of ground phosphate rock quality；
2nd, defluorinating agent is added into solution A, it is stirring while adding, continue to stir 1.5h after adding, stand, separation of solid and liquid, obtain
Solution B；The defluorinating agent is mixed by active silica 10g and sodium chloride 60g；The amount for adding defluorinating agent contains for ground phosphate rock
2 times of fluorine mole；
3rd, solution B is mixed with organic extractant and extracted, split-phase obtains oil phase X and aqueous phase Y, and oil phase X is stripped with pure water
Obtain phosphoric acid,diluted；The organic extractant is tributyl phosphate；
4th, milk of lime is slowly added into aqueous phase Y and adjusts pH value to 8, it is stirring while adding, 180min is reacted, filtering, is obtained
Filter residue D1 and Solution H, filter residue D1 are dried at 160-170 DEG C, obtain tricalcium phosphate；
5th, Solution H is heated to temperature as 70-80 DEG C, in the state of stirring, by rubbing for calcium chloride in Solution H and sulfuric acid
Your ratio is 1：2 add sulfuric acid, react 4h, filtering, obtain filter residue E1 and dilute hydrochloric acid solution, and filter residue E1 is dried at 110-120 DEG C,
Calcium sulfate crystal whiskers are obtained, phosphate rock-sulfuric acid powder in return to step 1 after dilute hydrochloric acid solution rectifying is concentrated.
Embodiment 9.
A kind of Application way of rock phosphate in powder, comprises the following steps：
1st, by rock phosphate in powder through crushing, it is levigate after obtained ground phosphate rock and hydrochloric acid at normal temperatures after stirring reaction 0.5h, solid-liquid
Separation, obtains phosphoric acid and the solution A of calcium chloride；Described rock phosphate in powder is phosphorus concentrate, and the granularity of ground phosphate rock is less than 40 after levigate
Mesh, concentration of hydrochloric acid 15wt%, addition are 1.5 times of ground phosphate rock quality；
2nd, defluorinating agent is added into solution A, it is stirring while adding, continue to stir 0.5h after adding, stand, separation of solid and liquid, obtain
Solution B；The defluorinating agent is mixed by active silica 5g and sodium chloride 40g；The amount for adding defluorinating agent contains for ground phosphate rock
1 times of fluorine mole；
3rd, solution B is mixed with organic extractant and extracted, split-phase obtains oil phase X and aqueous phase Y, and oil phase X is stripped with pure water
Obtain phosphoric acid,diluted；The organic extractant is tributyl phosphate；
4th, milk of lime is slowly added into aqueous phase Y and adjusts pH value to 7, it is stirring while adding, 90min is reacted, filtering, is filtered
Slag D1 and Solution H, filter residue D1 are dried at 70-80 DEG C, obtain tricalcium phosphate；
5th, Solution H is heated to temperature as 20-30 DEG C, in the state of stirring, by rubbing for calcium chloride in Solution H and sulfuric acid
Your ratio is 1：0.8 adds sulfuric acid, reacts 1h, filtering, obtains filter residue E1 and dilute hydrochloric acid solution, and filter residue E1 is dried at 70-80 DEG C,
Calcium sulfate crystal whiskers are obtained, phosphate rock-sulfuric acid powder in return to step 1 after dilute hydrochloric acid solution rectifying is concentrated.
Claims (6)
- A kind of 1. Application way of rock phosphate in powder, it is characterised in that：Comprise the following steps：（1）By rock phosphate in powder through crushing, it is levigate after obtained ground phosphate rock and hydrochloric acid at normal temperatures after 0.5~6h of stirring reaction, solid-liquid Separation, obtains phosphoric acid and the solution A of calcium chloride；Described rock phosphate in powder is mid low grade phosphate rock stone or phosphorus concentrate, the phosphorus after levigate The granularity of miberal powder is less than 40 mesh, and concentration of hydrochloric acid is 15~37wt%, and addition is 1.5~4 times of ground phosphate rock quality；（2）Defluorinating agent is added into solution A, it is stirring while adding, continue 0.5~2h of stirring after adding, stand, separation of solid and liquid, obtain Solution B；The defluorinating agent calculates by weight, is made up of active silica 0.5-1.5 parts and sodium chloride 4-8 parts；（3）Solution B is mixed with organic extractant and extracted, split-phase obtains oil phase X and aqueous phase Y, and oil phase X is stripped with pure water Phosphoric acid,diluted；The organic extractant is one or more of n-butanol, isoamyl alcohol, diisopropyl ether or tributyl phosphate；Or to molten Milk of lime is slowly added in liquid B and adjusts pH value to 1.6~2.8, it is stirring while adding, continue 1~4h of stirring after adding, filter, obtain To filter residue A1 and solution C, filter residue A1 is dried at 70~170 DEG C, obtains fertilizer calcium hydrophosphate；（4）Cleaner is added into solution C, it is stirring while adding, continue 0.5~3h of stirring after adding, filter, obtain solution D；Institute State cleaner to calculate by weight, be made up of vulcanized sodium 0.5-1.5 parts and disodium ethylene diamine tetraacetate 10-20 parts；（5）Solution D is heated to 20~80 DEG C, heated while stirring, be slow added into calcium containing compound adjust pH value to 4.5~ 6,2~6h is reacted, filtering, obtains filter residue B1 and solution F, filter residue B1 is dried at 70~170 DEG C, obtains calcium hydrophosphate fodder； Or by the molar ratio of phosphorus in solution D and melamine it is 0.5-1.5：0.5-4 adds solid melamine, reacts 0.5~3h Afterwards, catalyst is added, continues 0.5~5h of reaction, then is warming up to 80~160 DEG C, adds melamine mole 0.5~10 Reagent again, continuing 0.4~5h of stirring reaction, filtering, obtain filter residue C1 and solution G, filter residue C1 is dried at 70~170 DEG C, Obtain phosphorus-nitrogen composite combustion inhibitor, the reagent is one in bisphenol-A, phosphoric acid, urea, cyanuric acid, pentaerythrite or season pentanediol More than kind；（6）Milk of lime is slowly added into aqueous phase Y, solution F or solution G and adjusts pH value to 7-8, stirring while adding, reaction 90 Min~180min, filtering, filter residue D1 and Solution H are obtained, filter residue D1 is dried at 70~170 DEG C, obtains tricalcium phosphate；（7）Solution H is heated to temperature as 20~80 DEG C, in the state of stirring, by calcium chloride in Solution H and mole of sulfuric acid Ratio is 1：0.8~2 adds sulfuric acid, reacts 1~4h, filtering, obtains filter residue E1 and dilute hydrochloric acid solution, filter residue E1 is 70~170 Dried at DEG C, obtain calcium sulfate crystal whiskers, return to step after dilute hydrochloric acid solution rectifying is concentrated（1）Middle phosphate rock-sulfuric acid powder.
- 2. the Application way of rock phosphate in powder according to claim 1, it is characterised in that：Step（2）The middle amount for adding defluorinating agent For 1~4 times of the fluorine-containing mole of ground phosphate rock.
- 3. the Application way of rock phosphate in powder according to claim 1, it is characterised in that：Step（4）The middle amount for adding cleaner For ‰~8wt of 3wt ‰ of ground phosphate rock quality.
- 4. the Application way of rock phosphate in powder according to claim 1, it is characterised in that：Step（5）Described in calcic chemical combination Thing is one or more of lime stone, calcite, quick lime or white lime.
- 5. the Application way of rock phosphate in powder according to claim 1, it is characterised in that：Step（5）Described in catalyst be One or more of urea, ammonia contracting urea, hydrazine hydrate, ethylene urea, ethyl carbamide or MU.
- 6. the Application way of rock phosphate in powder according to claim 5, it is characterised in that：The addition of the catalyst is melamine The 0.2~20% of quality.
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